N-halo-3-morpholinone

ABSTRACT

1. A COMPOUND OF THE FORMULA   1-X,2-(O=),5-R1,5-R2,6-R3,6-R4-MORPHOLINE   WHEREIN X IS CHLORINE OR BROMINE, R1 AND R3 ARE EACH HYDROGEN, A TERTIARY ALKYL OF 1-4 CARBON ATOMS, OR PHENYL, AND R2 AND R4 ARE EACH HYDROGEN OR A TERTIARY ALKYL OF 1-4 CARBON ATOMS.

nited States Patent O 3,850,920 N-HALO-3-MORPHOLINONE Wilhelm E. Walles,Midland, Mich., assignor to The Dow Chemical Company, Midland, Mich. NoDrawing. Original application Oct. 30, 1967, Ser. No. 679,227, nowPatent No. 3,591,601, dated July 6, 1971. Divided and this applicationJan. 4, 1971, Ser. No.

Int. Cl. C07d 87/30 US. Cl. 260247.7 J 2 Claims ABSTRACT OF THEDISCLOSURE The N-chloro and N-bromo derivatives of 2-oxazolidinone,2-morpholinone, 2-oxazinidinone, and the corresponding hydrocarbonsubstituted compounds are prepared by halogenation, using a halogenatedisocyanuric acid as the halogenating reagent. These N-halo compounds aregermicides and bleaching agents.

CROSS-REFERENCE TO RELATED APPLICATION This is a division of mycopending application Ser. No. 679,227, filed Oct. 30, 1967 now US. Pat.3,591,601, dated July 6, 1971.

BACKGROUND OF THE INVENTION This invention relates to new chemicalcompounds and to a process whereby these and similar compounds areprepared. It relates particularly to certain new N-halo heterocyclicimides and to a method for preparing these and analogous knowncompounds.

SUMMARY OF THE INVENTION The new compounds of this invention are N-halooxygen-nitrogen heterocyclic imides having the structure where R and Rare each alkyl radicals,or R and R together form a heterocyclic' ring,are conveniently prepared by reacting the corresponding non-halogenatedcarboxamide with 'a halogenated isocyanuric acid as the source ofhalogen. Mono-, di-, or. trihalogenated isocyanuric acid, for example,chloroisocyanuric acid, dichloroisocyanuric acid, trichloroi'socyanuricacid, bromoisocyanuric acid, or tribromoisocyanuric acid can be used asthe halogenating reactant. The exothermic reaction can be carried outmerely by contacting the reagents at ambi ent temperature in a liquidmedium.

3,850,920 Patented Nov. 26, 1974 "ice DETAILED DESCRIPTION acidbyproduct is relatively insoluble and so is easily separated byfiltration of the reaction mixture. Since the halogenated cyanuric acidreacts to the extent that it is present or until halogenation of thecarboxamide is complete, the proportions of reactants are notcriticaL'but it is usually most convenient to employ at least oneequiva-. lent of halogen as contained in the halogenated isocyanuricacid per mole of amide group to be halogenated.

Halogenation may also be accomplished by known means, e.g., by reactingthe carboxamide with a hypohalite or free halogen in the presence of abase. However, the above-described transhalogenation method offer goodyields and is generally more convenient to use.

This prior art process usually involves a distillation to separate theproduct and so it is unsuitable for making the present compounds whichare thermally unstable. The N-bromo amides can also be prepared byreacting the corresponding N-chloro amide with an inorganic bromide in awater-immiscible organic solvent system as described in Example 8. Thislatter process is further described and claimed in my copendingapplication Ser. No. 679,254, filed Oct. 30, 1967, now abandoned.

The new compounds of this invention are useful in various applicationswhere positive halogen is of advantage. Thus, these compounds can serveas active ingredicuts in sanitizing and bleaching compositions. They canbe used as initiators of polymerizations such as those taught by Taberin US. 3,061,593. They are also useful, particularly the compounds whereA in the general formula is oxygen, as reagents causing rapiddecomposition reactions when contacted with alcohols, alkylamines, anddialkyl sulfoxides as taught in copending application of Walles andNagy, Delayed Action Explosives, Ser. No. 679,208, filed Oct. 30, 1967,now U.S. Pat. 3,468,674. The unusually high solubility of these newcompounds in chlorinated solvents makes them of particular interest inseveral of the above applications.

Example 1 A mixture of 35.7 g. of 5-methyl-2-oxazolidinone and 27.4 g.of trichloroisocyanuric acid was stirred together in a glass beaker. Themixture warmed rapidly to about 98 C., then cooled to form a thickslurry of fine white crystals. The slurry was filtered to obtain 26 g.of a clear yellow liquid. Theh filter cake was washed with benzene andthe benzene was evaporated from the washings to obtain another 9 gramsof the same liquid. The filter cake was dried and identified as purecyanuric acid. The liquid product was identified by infraredspectroscopic examination and elemental analysis as N-chloro-5-methyl-2-oxazolidinone. Found (average of two determinations): 29.5% C, 3.36 H,12.1% N, 28.8% C1. Calculated: 29.6% C, 3.32% H, 11.5% N, 29.2% C1. Thiscompound had a freezing point of 22 C. and it decomposed explosively atabout C.

Example 2 To a stirred slurry of 200 g. of trichloroisocyanuric acid in500 ml. of methylene chloride there was added dropwise 174.2 g. of5-methyl-2-oxazolidinone. The temperature of the reaction mixture rosefrom about 25 C. to 44 C. during the addition. The fine whiteprecipitate of cyanuric acid was filtered from the reaction mixture andthe methylene chloride was evaporated under reduced pressure to obtain225 g. of clear, nearly colorless N- chloro-5-methyl-2-oxazolidinone.

3 Example 3 99.2 g. of -ethyl-2-oxazolidinone with 100 g. oftrichloroisocyanuric acidin 400 ml. of methylene chloride. A yield of114 g.ofN-chloro-5-ethyl-2=oxazolidinone was isolated and identified asdescribed above. The product was a-clear, nearly colorless liquid whichdecomposed at l-l30 C. Found (average of two determinations): 39.4% C,5.15% 'H, 9.85% N, 23.5% Cl. Calculated: 40.1% C, 5.39%:1-1, 9.36% N,23.7% Cl.

v Exampl'4 By-the procedure of Examples 2- and 3, 60 grams of 2-oxazolidine was reacted with 80 g. of trichloroisocyanuric acid inmethylene chloride. 'After the solid cyanuric acid wasfiltered'from thereaction mixture, the filtrate was freed'of methylene chloride byevaporation to obtain 82.0 g. of white solid, mp 65'-70 C., decomposedat 175- 180- C.''T.his product was identified as before as N- chloro-2oxazolidinone..Elemental analysis showed (average of twodeterminations): 29.5% C, 3.36% H, 12.14% N, 28.8% C1. These results arevery close to the theoreticalf'values. l

' Example 5 w-Aslurry of 100 g. of trichloroisocyanuric, acid in 400 ml.ofmethyl ene chloride was stirred while 87.1 g. of 3- morpholinone wasadded portionwise over about one hour. The reaction mixture temperatureroseto about its reflux point during the addition. The chlorinatedproduct was isolated as in the foregoing examples to obtain 114 g. ofwhite crystals, identified by infrared spectroscopic examination andelemental analysis as N-chloro-3-morpholinone. This product melted at100-105 C. and decomposed explosively when heated to 115 C.

Example 6 Example 7 The procedure of Example 5 was employed to react73.2 g. of 2-pyrrolidinone with 100 g. of trichloroisocyanuric acid in400 ml. of methylene chloride; The filtrate from the resulting reactionmixture was heated to C. under reduced pressure to remove the solventthereby obtaining as a residue 96 g. of white crystals which wereidentified by the usual infrared spectroscopic examination and elementalanalysis as N-chloro-2-pyrrolidinone, m.p. 33-37 C., decomposed at 130C.

. Example 8 A slurry of 232 g. of trichloroisocyanuric"acid in 1000 g.of methylene chloride was stirred while 100 g. of 4-methyl-2-imidazolidinone in 800 g. of methylene chloride was added, thetemperature of the mixture rising to 39 C. during the addition. Uponworking up the reaction mixtureas previously described, there wasobtained 114 g. of

chloro-,4-.methyl-2 imidazolidinone, a clear yellow oil with an odor offree chlorine. The impure product'was unstable and exploded on standingfor several hours. Y

4 Example '9 A solution of 67.5 g. of N-chloro-5-methyl 2-oxazolfldinone in 200 ml. of methylene chloride was vigorously 4 stirred with asolution of 51.5 g. of sodium bromide i ml. of water. After tenminutes-of agitation, thela-yers were separated and the water layer wasdiscarded. Evaporation of solvent from the methylene chloride layeryielded 75 g. of N-brorno-5-methyl-2-oxazolidinone as pure Whitecrystals, m.p; 55C. The identity of the product was confirmed 'byelemental analysis-and infrared spectroscopic examination. I i Accordingto a procedure such as shown by the tore going examples,N.-chloro-5-phenyl-2 oxazolidinone is pre pared by reacting thenon-halogenated compound .with trichloroisocyanuric acid. In a similarWay','there are obtained N-halo compounds such asN-chloro-4,S-dimethyl-2-oxazolidinone;N-bromo-4,5-diphenyl-Loxazolidinone, 5-butyl-N bromo-Z-oxazolidinone,N-chloro-Z-oxazinidinone, N-b romo-S ,6-dimethyl-Z-oxazinidinone,N-bromo-4-eth'yl-3 morpholinone V p and the like by transhalogenationof-the parent -;com-. pounds as shown above. These compounds havephysical and chemical properties closely similar to-thosepfthe relatedcompounds shown in the examples. In the same way, aliphatic of'op'enchain secondary carboxamides such as N-methylacetamide, N-ethylbutyfiamide, and the like are converted to their N-phloroand N-bromoderivatives as shown inExample 1 0. I

I Example 10 1. A compound of the formula c Rx 0 R c cin wherein X ischlorine or bromine, R and R ,.areea'ch hydrogen, a tertiary alkyl of.1-4 carbon'aton 1s,.orv phenyl, and R and,R are each hydrogen or atertiary alkyl of 1-4 carbon atoms. 2 The compound of Claim 1 wherein R,,"R 1 R and g 4 are each hydrogen and X is chlorine and the com: poundis N-chloro-3-morpholinone.

References Cited UNITED STATES --BATENTS 2,013,791 9/1935 Sachs 260-:612,472,361 6/1949 Arsem 260+.583 2,971,959 2/1961 Waugh et al. 260.3 09.52,971,960 -2/1-961 Waugh et al. 260-309 5 DONALDIG. DAUS, PrimaryExaminer. J. TovAR, Assistant Examiner ZZZ v UNITED STATES PATENT OFFICE7 CERTIFICATE OF CORRECTION Patent 3.850.920 Dated November 26, 1974Inventor(s) Wilhelm E Walles It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Col. 2, line 39, delete "3,468,674" and insert 3,465,674-- Col. 2, line57, following "3.36" i t Signed and sealed this let day of April 1975.

(SEAL) Attest:

C. MARSHALL DANN RUTH C. MASON Commissioner of Patents Attesting Officery and Trademarks

1. A COMPOUND OF THE FORMULA